Negative plate material for storage batteries



Patented Jan. 5, 1 954 NEGATIVE PLATE MATERIAL FOR STORAGE BATTERIESThomas P. McFarlane, Farmington, Conn., and Otto Konig, New York, N. Y.,assignors to National Lead Company, New York, N. Y., a. corporation ofNew Jersey No Drawing. Application September 2, 1950, Serial No. 183,081

7 Claims. 1

This invention relates to a negative platematerial for lead acid storagebatteries. More particularly it relates to a negative plate containinga. water-soluble synthetic organic expander material.

It is well known that when a storage battery is discharged at a highrate at low temperatures, the electrical output or capacity isconsiderably less than the theoretical output expected; It has beenrecognized that the performance of a battery is improved by the additionto the negative plate material of small amounts of carbon black, blancfixe and certain organic materials known as organic expanders. A numberof such organic materials have been proposed but the only effective oneshave been the natural lignin derivatives. Such materials have thedisadvantage of varying considerably in performance. This variation isrelated to the unknown composition of the active member in the naturalmaterial which thus far has remained unidentified. The resultingperformance of a battery in a cold discharge test, therefore, isdificult to standardize.

Recently a group of synthetic phenolic condensation products have beenproposed as organic expanders. Such resinous products are insoluble inwater, require to be pulverized after filtration and drying. and arecostly to manufacture. the performance of natural expanders in coldcapacity tests. While-this attempt to standardize the efiect obtained bypreviously unknown natural principles is interesting, the search forreliable synthetic organic expanders which will equal the performance ofthe natural expanders has continued.

It is an object of this invention to provide an efiective negative platematerial with reliable cold capacity characteristics. It is a furtherobject to provide a negative plate material containing known syntheticorganic addition agents which will give predictable and dependable coldcapacity performance.

We have found that a negative plate material containing certainwater-soluble synthetic organic compounds to be described contributetowards obtaining such reliable and dependable results. The principalorganic compounds employed in this invention may be described aswater-soluble sulfonated polycyclic substituted aliphatic compounds,wherein two or more sulfonated cyclic groups are linked together bymeans of an open aliphatic linkage in contrast to fused cyclicstructures. We have found thatv it is advantageous to employ togetherwith the Furthermore, they have not approached 2 above-mentionedcompounds a proportion of water-soluble hydroxyaryl sulfonate.

More particularly, the products of this invention comprise predominantlylitharge, which may as the term is used in this art, consist of leadmonoxide or suboxide and metallic lead containing the usual amountsofcarbon black and blanc fixe and a small proportion of a sulfonatedpolycyclic substituted aliphatic compound such as phenolphthaleinsulfonate or indigo sulfonate and also a small proportion of awater-soluble hydroxylaryl sulfonate such as S-hydroxy-quinoline5-sulfonic acid or l-naphthol 5-sulfonic acid.

It is economical to procure the phenolphthalein or the indigo and tosulfonate them. We have found that the organic compounds employed inthis invention must be water-soluble and, therefore, either the aciditself or the al-' kali metal salts of the sulfonic acid may beemployed.

The preparation of total organic material in the negative mix may varybroadly from about 0.1% to 1.0% by weight, the usual proportion beingbetween 0.2 and 0.6%. In employing the combination mentioned, from 1 to3 parts of the first mentioned organic agent, such as pl1eno1- phthaleinsulfonate or indigo sulfonate, is combined with one part of thehydroxyaryl sulfonate.

In order to illustrate the products of the present invention, thefollowing examples are offered wherein a standard negative plate basemix material was prepared by intimately dry mixing a finely divideduncalcined Barton litharge containing approximately 30% metallic lead,carbon black and blanc fixe in the proportions of 91 g. of carbon blackand 136 g. of blanc fixe per pounds of litharge and the blend of organicmaterial added thereto.

EXAMPLE I To 100 pounds of a finely divided Barton litharge containingcarbon black and blanc fixe as above described were added 272 g. of ablend of 2 parts sodium phenolphthalein sulfonate and. 1 part8-hydroxyquinoline 5-sulfonic acid. The active material was well mixedto disperse the dry constituents and a paste was then prepared by adding5200 ml. of water and 3200 ml. of sul fonic acid of 1.400 specificgravity. The resulting paste which contained about 0.6% of organicmaterials by weight was used to prepare negative plates which wereemployed in making storage batteries of a standard type.

EXAMPLE II Storage battery paste was prepared in a manner similar tothat described in Example I except that the 272 g. of blended organicmaterial contained 2 parts of sodium phenolphthalein sulfonate and 1part of sodium salt of l-naphthol -sodium sulphonate. The resultingpaste was then used in preparing negative plates which were employed inmaking standard storage ba t teries.

EXAMPLE III To 4 pounds of a finely divided Barton litharge and theusual blend of 0.2% carbon black, 0.3% blanc fixe by weight, were added3.6 g. or 0.2% of sodium indigo disulfonate and 3.6 g. or 0.2% of 1-naphthol 5-sodium sulfonate. A paste was prepared by adding 120 ml. ofsulfuric acid of specific gravity 1.400 and 208 ml. of water. The

resulting paste was employed in the negative plates of standardbatteries. The above batteries were employed in a number of tests incomparison to control batteries with no expander addition and with theaddition o'f'ia prior art natural expander. The results in min utes ofdischarge, according to the specifications of the Society of AutomotiveEngineers, are given in the following table:

It will be noted that the products listed in the above table which areexamples of the products of this invention, compare favorably to thebest natural products available today. This represents a considerableadvance in the art of employing known synthetic principles, thepossibilities of which are directed to more exact con-" trol andreliability.

While this invention has been described and illustrated by theembodiments shown, it is not intended to be strictly limited thereto andother variations and modifications may be employed within the scope ofthe following claims.

We claim:

1. Active material for negative lead storage and a small proportion of awater soluble sulbattery plates comprising predominantly lithargephonated polycyclic substituted aliphatic compound and a smallproportion of a compound selected from the group consisting o18-hydroxyquinoline 5-sulphuric acid, l-naphthol 5-su1- phonic acid andtheir alkali metal salts.

2. Active material for negative lead storage battery plates comprisingpredominantly litharge and a small proportion of a compound selectedfrom the group consisting of a phenolphthalein sulphonate, indigosulphonate and their alkali metal salts and. a small proportion of acompound selected from the group consisting of 8- hydroxyl-quinoline5-sulphonic acid, l-naphthol 5-sulphonic acid and their alkali metalsalts.

3. Active material according to claim 1 in which the sum of theproportions of the first mentioned compound and the second mentionedcompound amounts to between 0.1% and 1% by weight of the activematerial.

4. Active material according to claim 1 in which the sum of theproportions of the first mentioned compound and the second mentionedcompound amounts to between 0.1% and 1% by weight of the active materialand there are present from 1 to 3 parts of the first mentioned compoundfor each part of the second mentioned compound.

5. Active material for negative lead storage battery plate comprisingpredominantly litharge and about 0.6% sodium phenolphthalein sulphonateand 0.3% S-hydroxy-quinoline 5-sulphonic acid.

6. Active material for negative lead storage battery plate comprisingpredominantly litharge and about 0.6% sodium phenolphthalein sulphonateand 0.3% l-naphthol 5-sodium sulphonate.

7. Active material for negative lead storage battery plate comprisingpredominantly litharge and about 0.2% sodium indigo disulphonate and0.2% l-naphthol 5-sodium sulphonate.

THOMAS P. MCFARLANE. OTTO KONIG.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 1,460,422 Kohn July 3, 1923 2,233,281 Brown Feb. 25, 19412,514,415 Rasch July 11, 1950 2,540,446 Haayman et a1. Feb. 6, 1951FOREIGN PATENTS Number Country Date 20,596 Great Britain Apr. 13, 1895of 1894

1. ACTIVE MATERIAL FOR NEGATIVE LEAD STORAGE BATTERY PLATES COMPRISINGPREDOMINANTLY LITHARGE AND A SMALL PROPORTION OF A WATER SOLUBLESULPHONATED POLYCYCLIC SUBSTITUTED ALIPHATIC COMPOUND AND A SMALLPROPORTION OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF8-HYDROXYQUINOLINE 5-SULPHURIC ACID, 1-NAPHTHOL 5-SULPHONIC ACID ANDTHEIR ALKALI METAL SALTS.